CN108636425A - Ferronickel sulfide-graphene composite material, preparation method and application - Google Patents
Ferronickel sulfide-graphene composite material, preparation method and application Download PDFInfo
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- CN108636425A CN108636425A CN201810456931.0A CN201810456931A CN108636425A CN 108636425 A CN108636425 A CN 108636425A CN 201810456931 A CN201810456931 A CN 201810456931A CN 108636425 A CN108636425 A CN 108636425A
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- composite material
- sulfide
- nickel
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- graphene
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- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 76
- 229910000863 Ferronickel Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002243 precursor Substances 0.000 claims abstract description 41
- 238000004073 vulcanization Methods 0.000 claims abstract description 39
- 150000002815 nickel Chemical class 0.000 claims abstract description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000005864 Sulphur Substances 0.000 claims abstract description 16
- 239000011541 reaction mixture Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- 150000002505 iron Chemical class 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 6
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 45
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- -1 compound Alkene Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241001061225 Arcos Species 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910003210 Ni0.75Fe0.25 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- QJSRJXPVIMXHBW-UHFFFAOYSA-J iron(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Fe+2].[Ni+2] QJSRJXPVIMXHBW-UHFFFAOYSA-J 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/23—
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
An embodiment of the present invention provides ferronickel sulfide graphene composite material, preparation method and applications, wherein the atomic ratio of nickel, iron, sulphur in the ferronickel sulfide is followed successively by 0.75：0.25：2, iron atom is incorporated into a manner of impurity in nickel sulfide lattice.The present invention also provides the preparation methods of ferronickel sulfide graphene composite material, including：(1), graphene oxide is scattered in solvent, obtains graphene oxide dispersion；(2), nickel salt solution, iron salt solutions are mixed with graphene oxide dispersion, obtains reaction mixture；(3), the reaction mixture is reacted 9 18 hours at 100 180 DEG C, obtains composite material precursors；(4), the composite material precursors and sulphur powder are subjected to calcining vulcanization in an inert atmosphere.The ferronickel sulfide graphene composite material of the present invention, the ferronickel in sulfide take the existence form of impurity, have good oxygen evolution reaction catalytic activity.
Description
Technical field
The present invention relates to oxygen evolution reaction elctro-catalyst technical fields, more particularly to ferronickel sulfide-graphene composite wood
Material, preparation method and application.
Background technology
The problems such as resource exhaustion and environmental pollution caused by the use of fossil fuel getting worse, there is an urgent need to open by people
Send out novel energy, such as Hydrogen Energy.Water electrolysis hydrogen production is one of the effective means for obtaining hydrogen.Electrolysis water process includes two and half anti-
It answers, evolving hydrogen reaction (HER) and oxygen evolution reaction (OER).Wherein, the dynamic process of oxygen evolution reaction is slow, limits electrolysis water process
Efficiency.It is generally necessary to introduce oxygen evolution reaction elctro-catalyst to improve the rate of this process.Currently, optimal OER elctro-catalysts
It is RuO2And IrO2, but such noble metal catalyst is of high cost, scarcity of resources.Therefore, the base metal OER that exploitation is cheap, is easy to get
Elctro-catalyst is particularly significant.
Invention content
The embodiment of the present invention be designed to provide a kind of ferronickel sulfide-graphene composite material, preparation method and
Using.Specific technical solution is as follows：
Present invention firstly provides a kind of ferronickel sulfide-graphene composite material, nickel in the ferronickel sulfide,
Iron, sulphur atomic ratio be followed successively by 0.75：0.25：2, ferro element is incorporated into a manner of impurity in nickel sulfide lattice.
In certain embodiments of the present invention, the ferronickel sulfide is scattered in graphene surface.
In certain embodiments of the present invention, ferronickel sulfide exists in granular form.
The present invention also provides the preparation methods of ferronickel sulfide-graphene composite material above-mentioned, including：
(1), graphene oxide is scattered in solvent, be preferably dispersed in DMF, obtain graphene oxide dispersion；
(2), nickel salt solution, iron salt solutions are mixed with graphene oxide dispersion, obtains reaction mixture；Wherein, nickel
The molar ratio of salt and molysite is more than or equal to 3：1；Preferably (3-5)：1, more preferably 5：1；
(3), the reaction mixture is reacted 10-18 hours at 100-180 DEG C, is then detached, washed, is obtained
Composite material precursors；
(4), the composite material precursors and sulphur powder are subjected to calcining vulcanization in an inert atmosphere, the temperature for calcining vulcanization is
300-600 DEG C, the time for calcining vulcanization is 0.5-2 hours, and heating rate is 3-8 DEG C/min.
In certain embodiments of the present invention, the one kind or its group of nickel salt in nickel acetate, nickel nitrate, nickel chloride
It closes；The one kind or combinations thereof of molysite in ferric acetate, ferric nitrate, iron chloride.
In certain embodiments of the present invention, the ratio of the quality of the molal quantity and graphene oxide of the nickel salt is：
(0.016-0.04) mol/g, preferably (0.02-0.04) mol/g, more preferably 0.02mol/g.
In certain embodiments of the present invention, the composite material precursors and the mass ratio of the sulphur powder are 1:(20-
40)。
In certain embodiments of the present invention, step (3) is specially：Answer mixture anti-at 100-130 DEG C by described
It answers 9-14 hours, is continuously heating to react 1-4 hours at 150-180 DEG C.
In certain embodiments of the present invention, before step (3), further include：
Reaction mixture is stirred 2-8 hours at 50-90 DEG C, is then cooled down.
The present invention also provides the use that ferronickel sulfide-graphene composite material above-mentioned is used as oxygen evolution reaction elctro-catalyst
On the way.
The present invention has obtained ferronickel sulfide-graphite by the way that ferronickel sulfide and high conductivity substrate graphene is compound
Alkene composite material has good oxygen evolution reaction catalytic activity.Meanwhile preparation method provided by the invention, make graphene oxide
Reduction and the sulfidation of transition metal occur simultaneously, preparation process is easier.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Obtain other attached drawings according to these attached drawings.
Fig. 1 is the XRD diagram corresponding to embodiment 1-3 and comparative example 1, wherein a-c is followed successively by embodiment 2, embodiment 1, reality
Apply the XRD diagram of the composite material precursors prepared by example 3；D-f be followed successively by embodiment 2,
The XRD diagram of composite material prepared by embodiment 1, embodiment 3；G is NiS prepared by comparative example 12The XRD of-GN
Figure；
Fig. 2 is the Raman spectrogram of the composite material after composite material precursors prepared by embodiment 1 and vulcanization, wherein a is
The Raman spectrogram of composite material precursors, b are the Raman spectrogram of the composite material after vulcanization；
Fig. 3 is the XPS spectrum figure of the composite material after composite material precursors prepared by embodiment 1 and vulcanization, wherein in Fig. 3
(a)-(c) indicates the Fe 2p spectrograms of composite material precursors successively, Ni 2p spectrograms, C 1s spectrograms, (e)-(h) tables successively in Fig. 3
Show the Fe 2p spectrograms of the composite material after vulcanization, Ni 2p spectrograms, C 1s spectrograms, S 2p spectrograms, before (d) being expressed as composite material
The full spectrum of composite material after body and vulcanization；
Fig. 4 is the SEM photograph corresponding to embodiment 1-3, wherein (a)-(c) is followed successively by embodiment 2, embodiment 1, implements
The SEM photograph of composite material precursors prepared by example 3；(a ')-(c ') is followed successively by embodiment 2, embodiment 1, prepared by embodiment 3
Composite material SEM photograph；
Fig. 5 is the TEM photos of the composite material after composite material precursors prepared by embodiment 1 and vulcanization, wherein in Fig. 5
(a) it is the TEM photos of composite material precursors, GO indicates graphene oxide in figure,
NiFeLDH indicates composite material precursors, and (b) be the TEM photos of the composite material after vulcanizing in Fig. 5, GN tables in figure
Show graphene, (NiFe) S2Indicate ferronickel sulfide；(c) is the HRTEM photos of the composite material after vulcanization in Fig. 5；
Fig. 6 is composite material (NiFe) S prepared by embodiment 12The SEM photograph of-GN-0.2 and corresponding Fe, Ni, C, S member
Element distribution and each element molar content；
Fig. 7 A are RuO2、(NiFe)S2-GN-0.16、(NiFe)S2-GN-0.2、(NiFe)S2-GN-0.4,NiS2-GN、
The polarization curve of NiFe LDH-GO-0.2 and glass-carbon electrode (GC), wherein NiFe LDH-GO-0.2 indicate prepared by embodiment 1
Composite material precursors, RHE indicate reversible hydrogen electrode；
Fig. 7 B are RuO2、(NiFe)S2-GN-0.16、(NiFe)S2- GN-0.2 and (NiFe) S2The Ta Feier of-GN-0.4 is bent
Line chart；
Fig. 7 C are (NiFe) S2-GN-0.16、(NiFe)S2-GN-0.2、(NiFe)S2- GN-0.4 and NiS2The impedance of-GN
Figure, frequency range 105Hz to 0.1Hz, current potential 1.6V (vs.RHE), Z ' indicate that real part, Z " indicate imaginary part；
Fig. 7 D are (NiFe) S2The constant potential curves of-GN-0.2 at overpotential 350mV；
Fig. 8 is (NiFe) S2The polarization curve of the 1st circle (a) and the 500th circle (b) of-GN-0.2.
Specific implementation mode
The present invention provides a kind of ferronickel sulfide-graphene composite material, nickel, iron, sulphur in the ferronickel sulfide
Atomic ratio be followed successively by 0.75：0.25：2, in ferronickel sulfide, ferro element is incorporated into nickel sulfide crystalline substance in a manner of impurity
In lattice.In some embodiments, ferronickel sulfide is scattered in graphene surface.In other specific implementation modes,
In granular form, especially the form of nano particle exists ferronickel sulfide.
Ferronickel sulfide-graphene composite material prepared by the present invention has good oxygen evolution reaction catalytic activity,
It may be used as oxygen evolution reaction elctro-catalyst.
Herein, the size that described " nano particle " can be regarded as at least one dimension of the particle is nanoscale, such as
Between 1-100nm.
The method that the present inventor creatively uses " solvent heat-is high temperature vulcanized ", prepares ferronickel sulfide-graphite
Alkene composite material, referred to as (NiFe) S2-GN.Specifically, design generates stratiform nickel iron hydroxide letter by solvent thermal reaction
Claim NiFe LDH, nickel, ferro element is introduced into LDH laminates, and in LDH laminates, two kinds of nickel, iron elements are in impurity shape
State, and make nickel, iron oriented growth, it is evenly distributed, nickel, the molar ratio of iron component are controllable.Further, dexterously pass through step height
Warm vulcanization reaction, makes that graphene oxide is reduced to the process of graphene and the sulfidation of nickel, iron occurs simultaneously；There to be analysis oxygen
The ferronickel sulfide of catalytic activity, referred to as (NiFe) S2, compound with the success of high conductivity substrate graphene；Finally obtain ferronickel
Sulfide-graphene composite material.
Based on above-mentioned mentality of designing, the present invention provides a kind of preparation sides of ferronickel sulfide-graphene composite material
Method comprising：
(1), graphene oxide is scattered in solvent, be preferably dispersed in DMF, obtain graphene oxide dispersion；
(2), nickel salt solution, iron salt solutions are mixed with graphene oxide dispersion, obtains reaction mixture；Wherein, nickel
The molar ratio of salt and molysite is more than or equal to 3：1；Preferably (3-5)：1, more preferably 5：1；
(3), the reaction mixture is reacted 10-18 hours at 100-180 DEG C, is detached, is washed, obtained compound
Material precursor；
(4), the composite material precursors and sulphur powder are subjected to calcining vulcanization in an inert atmosphere, the temperature for calcining vulcanization is
300-600 DEG C, the time for calcining vulcanization is 0.5-2 hours, and heating rate is 3-8 DEG C/min.
In specific implementation process, step (1) if in solvent can disperse graphene oxide, to obtain oxidation stone
Black alkene dispersion liquid；Usually, DMF (N, N ' dimethylformamide) dispersion graphene oxides may be used.It is specific at some
In embodiment, the ratio of graphene oxide and solvent can be 0.5-2mg/mL；Such as 1mg/mL.Preferably, specific real
During applying, after graphene oxide is scattered in solvent, it is ultrasonically treated, it usually, can ultrasound 30-60 minutes；With
Get more quickly to graphene oxide dispersion.It should be noted that the preparation method of graphene oxide is the prior art, this hair
It is bright herein without limit.
For the ratio of nickel salt and molysite, inventor has found, the nickel, iron atom ratio in the ferronickel sulfide prepared are 3：
1；Based on this, in specific implementation process, the molar ratio of nickel salt and molysite is preferably greater than to be equal to 3：1；More preferably (3-5)：
1, also preferably 5：1.Excess of the nickel salt in preferred scope, can improve the yield of ferronickel sulfide.
In certain embodiments of the present invention, the one kind or its group of nickel salt in nickel acetate, nickel nitrate, nickel chloride
It closes.In certain embodiments of the present invention, the one kind or combinations thereof of molysite in ferric acetate, ferric nitrate, iron chloride.
In specific implementation process, nickel salt can be configured to nickel salt solution, iron salt solutions in advance with molysite；Specifically, may be used
Nickel salt and iron salt dissolved are formed nickel salt solution, iron salt solutions in or mixtures thereof DMF, water；More specifically, Ke Yipei
It is made as nickel salt DMF solution, the molysite DMF solution of a concentration of (0.16-0.4) M, 1M=1mol/L.In some implementations of the present invention
In mode, the ratio of the molal quantity of nickel salt and the quality of graphene oxide is：(0.016-0.04) mol/g, preferably (0.02-
0.04) mol/g, more preferably 0.02mol/g.The molal quantity of molysite can by the molar ratio and nickel salt of nickel salt and molysite with
The ratio of graphene oxide determines, such as by the molar ratio of nickel salt and molysite is 5：1, the molal quantity and graphite oxide of nickel salt
The ratio 0.02mol/g of the quality of alkene is determined.
In certain specific embodiments of the invention, before step (3), further include：
Reaction mixture is stirred 2-8 hours at 50-90 DEG C, is then cooled down.It, can by stirring at a certain temperature
To promote nickel ion and iron ion to pass through the combination of electrostatic interaction and graphene oxide and the crystallization nucleation of NiFe LDH.
In certain specific embodiments of the invention, step (3) is specially：Answer mixture at 100-130 DEG C by described
Lower reaction 9-14 hours is continuously heating to react 1-4 hours at 150-180 DEG C.Inventor has found, when using this two-period form
When temperature-rise period, it is more advantageous to regulation and control or improves the crystallinity of product.
In specific implementation process, the solvent thermal reaction of step (3) can be realized in water heating kettle.It had been embodied
Cheng Zhong can be shifted if the whole system of reaction mixture is too small relative to the volume of water heating kettle by reaction mixture
To after water heating kettle, then add a part of solvent (such as DMF) into water heating kettle and/or water is carried to adjust the compactedness of water heating kettle
The pressure of high hydrothermal system.In certain embodiments of the present invention, after adding solvent and water to water heating kettle, meet final
The ratio of solvent and water in water heating kettle is essentially (0.8-1.2):1.
In certain specific embodiments of the invention, step (3) after reaction, be centrifuged, and will point
Composite material precursors crude product with water and ethyl alcohol from gained alternately wash, and composite material precursors are obtained after dry；Certainly, in addition to
Ethyl alcohol, organic solvent that can also be volatile, less toxic using acetone etc. slightly produce to replace ethyl alcohol to wash gained composite material precursors
Object.
In certain specific embodiments of the invention, step (4) may be used tube furnace and be vulcanized, and be answered what is weighed
Condensation material precursor and sulphur powder (S powder) are respectively placed in the both ends of porcelain boat, calcine in sulfidation and are continually fed into inert gas, such as argon
Gas；Wherein S powder is placed in weather.S powder of the present invention is elemental sulfur, such as sublimed sulfur.Inventor has found, in calcining sulphur
The temperature of change is 300-600 DEG C, and the time for calcining vulcanization is 0.5-2 hours, in the case that heating rate is 3-8 DEG C/min, institute
The state of cure (vulcanization) of nickel, iron in obtained sulfide is substantially consistent.In certain specific embodiments of the invention, institute
The mass ratio for stating composite material precursors and the sulphur powder is 1:(20-40).The dosage of sulphur powder can be according to molysite, the nickel being added
The amount of salt adjusts；Specifically, molysite, nickel salt amount it is more when, sulphur powder increases accordingly, molysite, nickel salt amount it is few when, sulphur powder phase
The reduction answered.
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
First, the preparation method of graphene oxide is illustrated.Graphene oxide employed in the present invention can be by
Prepared by improved Hummer methods, detailed process includes：By natural flake graphite (5g), the concentrated sulfuric acid (230mL, 98%) and nitre
Sour sodium (NaNO3, 5g) and mixing, it is cooling under condition of ice bath not deactivate glass bar stirring, after mixing, it is slowly added to Gao Meng
Sour potassium (KMnO4, 30g), control temperature of reaction system.Then reaction vessel is placed in 35 DEG C or so of water bath with thermostatic control, is stirred
After 30min, deionized water (460mL) is added, oil bath, control reacting liquid temperature is at 98 DEG C or so.Continue to stir 15min, then
A large amount of deionized water (1.4L) washing is added, while hydrogen peroxide (30%H is added2O2, 25mL), at this moment solution is from dark brown discoloration
For vivid yellow.Filtering, is used in combination dilute hydrochloric acid (1 after still aging：10 volume ratios, 2L) product is washed.Use deionization
Water fully washs until without SO in filtrate4 2-(BaCl2Solution detects).65 DEG C are air-dried, closed preservation.
The preparation embodiment of ferronickel sulfide-graphene composite material
Embodiment 1
0.008g graphene oxides are scattered in 8mL DMF (N, N ' dimethylformamide), and ultrasound is formed evenly dispersed
Liquid.It is added with stirring the DMF solution and 160 μ L 0.2M Fe (NO of 800 μ L 0.2M nickel acetates3)3·9H2The DMF solution of O, 85
DEG C oil bath 4h.After system cooling, 8mL DMF and 16mL distilled water is added, mixture is transferred in 100mL reaction kettles, 120 DEG C
12h is reacted, 160 DEG C of reaction 2h are continuously heating to.After kettle is cooled to room temperature, crude product with water and ethyl alcohol washing centrifuge,
60 DEG C of dryings.Obtain composite material precursors.
Vulcanized using tube furnace, weighs 0.015g composite material precursors and 0.5g S powder is respectively placed in the two of porcelain boat
End, wherein S powder are placed in weather, 400 DEG C of calcining 1h, 5 DEG C/min of heating rate, and argon gas is continually fed into calcination process.It obtains
Sulfur product, i.e. ferronickel sulfide-graphene composite material (referred to as composite material), are denoted as (NiFe) S2-GN-0.2。
Embodiment 2
Ferronickel sulfide-graphene composite material is prepared according to the method for embodiment 1, is existed with the difference of embodiment 1
In：The nickel acetate and Fe (NO being added3)3·9H2A concentration of 0.16M of O；Gained sulfur product is denoted as (NiFe) S2-GN-
0.16。
Embodiment 3
Ferronickel sulfide-graphene composite material is prepared according to the method for embodiment 1, is existed with the difference of embodiment 1
In：The nickel acetate and Fe (NO being added3)3·9H2A concentration of 0.4M of O；Gained sulfur product is denoted as (NiFe) S2-GN-
0.4。
Embodiment 4
Ferronickel sulfide-graphene composite material is prepared according to the method for embodiment 1, is existed with the difference of embodiment 1
In：The temperature of calcining vulcanization is 300 DEG C, and the time for calcining vulcanization is 2 hours, and heating rate is 3 DEG C/min.
Embodiment 5
Ferronickel sulfide-graphene composite material is prepared according to the method for embodiment 1, is existed with the difference of embodiment 1
In：The temperature of calcining vulcanization is 600 DEG C, and the time for calcining vulcanization is 0.5 hour, and heating rate is 8 DEG C/min.
Embodiment 6
Ferronickel sulfide-graphene composite material is prepared according to the method for embodiment 2, is existed with the difference of embodiment 2
In：The dosage of S powder is 0.3g.
Embodiment 7
Ferronickel sulfide-graphene composite material is prepared according to the method for embodiment 3, is existed with the difference of embodiment 3
In：The dosage of S powder is 0.6g.
Comparative example 1
Nickel sulfide-graphene composite material is prepared according to the method for embodiment 1, difference from example 1 is that：
Only it is added without Fe (NO3)3·9H2The DMF solution of O；Nickel sulfide-graphene composite material of gained is denoted as：NiS2-GN。
The characterization of ferronickel sulfide-graphene composite material and test
1, XRD analysis
X-ray powder diffraction instrument (the model produced using company of Dutch Panaco company：X Pert PRO MPD) to this
The composite material prepared in inventive embodiments 1-3 and comparative example 1 carries out X-ray diffraction analysis, and analysis result is as shown in Figure 1；Point
Radioactive source during analysis is Cu-Ka, and it is 0.017 ° to measure step-length, and sweep time is 10 seconds/step.
Fig. 1 is NiS prepared by composite material precursors, corresponding sulfur product and the comparative example 1 prepared by embodiment 1-32-
The XRD diagram of GN.From figure 1 it appears that the composite material precursors (a-c in Fig. 1) prepared by embodiment 1-3 are in d=0.79nm
The diffraction maximum for occurring (003) and (006) face successively with d=0.39nm illustrates that interlamellar spacing is 0.79nm, is CO3 2-The LDH of intercalation
(layered double hydroxide), it was confirmed that composite material precursors have layer structure.After vulcanization, NiS2- GN (g in Fig. 1) is 2
θ=27.2 °, 31.5 °, 35.3 °, 38.8 °, 45.1 °, 53.5 °, 56.1 °, 58.6 ° and 61.0 ° there are a series of diffraction maximums, with
Standard card NiS2(PDF 65-3325) is consistent, wherein 31.5 °, 35.3 ° and 53.5 ° are respectively NiS2(200), (210)
(311) the corresponding diffraction of crystal face.Ferronickel sulfide-graphene composite material (d-f in Fig. 1) prepared by embodiment 1-3 with
NiS2The diffraction maximum shape of-GN samples (g in Fig. 1) is close, but to high angle micro-shifting occurs for all diffraction peaks, wherein
(200), the corresponding diffraction maximum micro-shifting of (210) and (311) crystal face is to 31.9 °, 35.8 ° and 54.2 °.Further analysis shows, Fe3+
And Ni2+Ionic radius is respectively 0.055nm and 0.069nm, therefore movement of the peak position to high angle is due to the smaller Fe of radius3 +Mix NiS2Lattice in.XRD spectrum does not observe the diffraction maximum of vulcanization iron phase, further proves that Fe is incorporation NiS2Crystalline substance
Lattice.
2, Raman spectrum analysis
The laser co-focusing Raman scattering spectrometer (model produced using French Horiba Jobin Yvon companies：
LabRAM Aramis) Raman spectrum analysis is carried out to the composite material after the composite material precursors of the preparation of embodiment 1 and vulcanization,
Raman spectrum is as shown in Figure 2；Using the solid state laser of 532nm as light source in analytic process.A can be seen that multiple from Fig. 2
Condensation material precursor is in 1354cm-1And 1602cm-1There are two peaks, is attributed to the D bands and G bands of carbon material respectively.After vulcanization, such as
In Fig. 2 shown in b, respectively in 1362cm-1And 1610cm-1Observe D bands and G bands in place.The intensity of D bands and G bands ratio, ID/IG, reflection
Orderly and unordered degree in carbon material crystal structure.With ID/IGThe reducing degree of the reduction of value, graphene oxide increases.It is multiple
The I of composite material after condensation material precursor and vulcanizationD/IGValue is respectively 1.08 and 1.00.After illustrating vulcanization, graphene oxide quilt
Successfully it is reduced to graphene.
3, XPS (x-ray photoelectron spectroscopy) is analyzed
X-ray photoelectron spectroscopy (the model produced using ThermoFisher companies of Britain：ESCSLAB250Xi) right
The composite material precursors of the preparation of embodiment 1 and the composite material after vulcanization carry out XPS analysis, using AlKl rays as X-ray
Source.XPS spectrum figure is as shown in Figure 3；
The full spectrum of composite material precursors confirms the presence of C, O, Fe and Ni element (in Fig. 3 (d)).In Fig. 3 (a),
The combination of 725.6eV and 712.6eV can correspond to Fe respectively3+Fe 2p1/2 and Fe2p3/2.In Fig. 3 (b), 873.9eV and
856.2eV is respectively belonging to Ni2+Ni 2p1/2 and Ni 2p3/2, remaining is satellites.(c) is that C 1s are composed in Fig. 3,284.7,
288.4,286.4 and 285.4eV corresponds to C-C/C=C, O-C=O, C=O and the C-O group in graphene oxide respectively.
Product (NiFe) S after vulcanization2- GN-0.2 removes C, O, outside Fe and Ni elements, there is also S elements (in Fig. 3 (d) and
(h)).From (e) in Fig. 3 as can be seen that vulcanization after product Fe 2p compared with composite material precursors, in conjunction with can be 707.5eV with
Two peaks of 720.3eV are attributed to the Fe2p3/2 and 2p1/2 of simple substance Fe respectively, it may be possible to due to the Fe during high temperature vulcanized3+
It is restored by carbon part.(f) is that the Ni 2p of product after vulcanizing are composed in Fig. 3, and the peak of 856.8eV and 875.2eV are belonging respectively to Ni2+'s
Ni 2p3/2 and Ni 2p1/2,881.1eV and 861.8eV can be attributed to Ni2+Satellites.In addition, in conjunction with can in 853.8eV and
Two peaks of 871.0eV are respectively Ni 2p3/2 and the Ni 2p1/2 of simple substance Ni, are equally since carbon restores Ni under high temperature2+It makes
At.It is compared with composite material precursors, O-C=O in the C 1s spectrums (Fig. 3 (g)) of product after vulcanization, the peak of C=O and C-O groups is all
It is apparent to weaken, illustrate that graphene oxide is reduced.(Fig. 3 (h)), 163.0eV and 164.0eV in the S 2p spectrograms of product after vulcanization
Two peaks correspond to S respectively2 2-S 2p3/2 and S 2p1/2.The peak of 168.8eV is to be exposed to partial oxidation in air by sample
At SO4 2-It causes.
4, electron microscope analysis
Using scanning electron microscope (SEM) to the product after the embodiment 1-3 composite material precursors prepared and vulcanization
Pattern is characterized, and the results are shown in Figure 4.NiFe LDH nanometer sheets grow and are covered in it can be seen from (a) and (b) in Fig. 4
Surface of graphene oxide, nanometer sheet grain size about 30-50nm.With the increase for the middle metal salt concentrations that feed intake, in Fig. 4 shown in (c), production
The density of LDH nanometer sheets increases in object, and gradually appears reunion tendency.After vulcanization, the pattern of composite material is rendered as irregularly
Particle, grain size is without significant change, as shown in Fig. 4 (a ')-(c ').
(NiFe) S after the composite material precursors prepared to embodiment 1 using transmission electron microscope (TEM) and vulcanization2-
The pattern of GN-0.2 further characterizes, and the results are shown in Figure 5.(a) can be seen that in composite material precursors in Fig. 5, NiFe
LDH nanometer sheets are uniformly embedded in graphene oxide substrate, and after vulcanizing it can be seen from (b) in Fig. 5, nanometer sheet is converted into
The irregular nano particle of pattern, the black particles in figure are to be scattered in the metal sulfide of graphene surface.The front and back grain of vulcanization
The grain size of son, which has no, to be substantially change, this is consistent with SEM results.(c) is (NiFe) S in Fig. 52The high-resolution transmission electricity of-GN-0.2
Mirror (HRTEM) photo, it will be clear that NiS from figure2Striped phase, fringe spacing 0.281nm, correspond to NiS2's
(200) crystal face.
5, energy disperse spectroscopy (EDS) elemental analysis and icp analysis
Elemental analyser (the model produced using German Brooker company：XFlash 6160) and German Spike analysis
Inductively coupled plasma atomic emission spectrometer (ICP-AES, the model of instrument company's production：SPECTRO ARCOS EOP)
The composite material prepared to embodiment 1 is analyzed, and Fig. 6 is (NiFe) S2The SEM photograph of-GN-0.2 and corresponding Fe, Ni,
C, S Elemental redistributions and each element molar content.The result shows that in composite material prepared by embodiment 1, there are Fe, Ni, C
With the elements such as S, and it is evenly distributed.Ni:Fe atoms number ratio is 2.96:1 (=4.12/1.39=2.96, Fig. 6).Pass through ICP points
Analysis is confirmed, is 3.04:1, close to 3:1, thus speculate Ni in composite material:Fe molar ratios are 3:1.Meanwhile EDS results are also
Show that the atom number ratio of metallic element (Fe and Ni) and S are 1:1.97, it may be determined that the composition formula of ferronickel sulfide is
(Ni0.75Fe0.25)S2.EDS elemental analyses and icp analysis test are carried out to embodiment 2-7, can be obtained same as Example 1
As a result.The present invention no longer repeats herein.
6, electrocatalysis characteristic
The composite material prepared using 1-3 of the embodiment of the present invention carries out its oxygen evolution reaction catalytic performance as catalyst
Test.It is the glass-carbon electrode of supported catalyst that test, which uses standard three electrode system, working electrode, is Pt plate electrodes to electrode,
Reference electrode is Hg/HgO electrodes.Working electrode preparation process is as follows：4mg catalyst is dispersed in 175 μ L isopropanols and 825 μ L water
In the mixed solvent, be added 40 μ L Nafion solutions (Shanghai Hesen Electric Co., Ltd, model |：Du Pont D520), ultrasound.With
Liquid-transfering gun pipettes 10 μ L dispersion liquids and is coated on glass-carbon electrode, 40 DEG C of drying.Electrolyte is the 1M KOH solutions of 50mL oxygen saturation.
Polarization curve result is as shown in Figure 7 A.RuO2(Sigma-Aldrich Chemical reagent Co., Ltd, product identification 238058) is made
For contrast material, fabulous catalytic performance is shown, current density reaches 10mAcm-2Overpotential (the η of Shi Suoxu10) be
242mV.Bare glassy carbon electrode hardly has catalytic activity.In three kinds of ferronickel sulfide-graphene composite materials, (NiFe) S2-
The η of GN-0.410For 380mV；(NiFe)S2- GN-0.16 and (NiFe) S2The η of-GN-0.210Respectively 317mV and 320mV, number
Value is close.To (NiFe) S2- GN-0.2, with the raising for applying current potential, current density rises rapidly, is significantly better than (NiFe) S2-
GN-0.16.The analysis oxygen performance of the composite material precursors of the preparation of embodiment 1 is tested simultaneously, and activity is than sulfur product (NiFe)
S2The poor activity of-GN-0.2 illustrates that vulcanizing treatment significantly improves the oxygen evolution reaction catalytic activity of material.Prepared by comparative example
NiS2The overpotential for oxygen evolution of-GN materials is high, and current density is low, and activity is poor, illustrates that the incorporation of Fe can significantly improve catalytic performance,
May be since the incorporation of Fe optimizes the electronic structure of material.
For the catalytic kinetics of further Electrode, Tafel curves have been carried out to the embodiment 1-3 composite materials prepared
Fitting, as a result as shown in Figure 7 B.The linear segment of curve Tafel equation models.
η=blogj+a
Wherein, η is overpotential, and j is current density, and b is Tafel slopes, and a indicates that current density is unit numerical value (1A/
cm2) when overpotential value.
(NiFe)S2- GN-0.16 and (NiFe) S2(Tafel slopes indicate current density with mistake to the Tafel slopes of-GN-0.4
Current potential increases and increased rate, this value are smaller, illustrates that the oxygen evolution kinetic of material is faster) it is respectively 98mV/dec and 115mV/
Dec, and (NiFe) S2The Tafel slopes of-GN-0.2 are less than RuO down to 61mV/dec, the value268mV/dec, illustrate three kinds of materials
In material, (NiFe) S2- GN-0.2 shows most fast oxygen evolution kinetic and catalytic activity.
Electrochemical impedance spectroscopy (EIS) research is carried out to material, as a result as seen in figure 7 c.(NiFe)S2The song of-GN-0.2
Line radius is less than (NiFe) S2- GN-0.16, (NiFe) S2- GN-0.4 and NiS2- GN illustrates material (NiFe) S2- GN-0.2 exists
There is lower charge transfer resistance and faster electron transfer rate in catalytic process, catalytic performance can be made to get a promotion.
Stability is to weigh one of the standard of catalyst performance.To (NiFe) S2- GN-0.2 is carried out surely under 1.55V current potentials
Qualitative test, as a result as illustrated in fig. 7d.After catalysis reaction carries out 10h, material still maintains 93% current density.Illustrate (NiFe)
S2- GN-0.2 has good stability.
Using cyclic voltammetry to (NiFe) S2- GN-0.2 has carried out 500 circle scannings, the η of material after scanning10Only increase
20mV still has higher catalytic activity (as shown in Figure 8), illustrates that the cyclical stability of material is preferable.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the scope of the present invention.It is all
Any modification, equivalent replacement, improvement and so within the spirit and principles in the present invention, are all contained in protection scope of the present invention
It is interior.
Claims (10)
1. ferronickel sulfide-graphene composite material, which is characterized in that the atomic ratio of nickel, iron, sulphur in the ferronickel sulfide
Example is followed successively by 0.75：0.25：2, ferro element is incorporated into a manner of impurity in nickel sulfide lattice.
2. ferronickel sulfide-graphene composite material as described in claim 1, which is characterized in that the ferronickel sulfide point
It dissipates in graphene surface.
3. ferronickel sulfide-graphene composite material as claimed in claim 1 or 2, which is characterized in that ferronickel sulfide with
Particle shape formula exists.
4. the preparation method of ferronickel sulfide-graphene composite material as claimed in any one of claims 1-3, feature exist
In, including：
(1), graphene oxide is scattered in solvent, be preferably dispersed in DMF, obtain graphene oxide dispersion；
(2), nickel salt solution, iron salt solutions are mixed with graphene oxide dispersion, obtains reaction mixture；Wherein, nickel salt with
The molar ratio of molysite is more than or equal to 3：1；Preferably (3-5)：1, more preferably 5：1；
(3), the reaction mixture is reacted 10-18 hours at 100-180 DEG C, is then detached, is washed, obtained compound
Material precursor；
(4), the composite material precursors and sulphur powder are subjected to calcining vulcanization in an inert atmosphere, the temperature for calcining vulcanization is 300-
600 DEG C, the time for calcining vulcanization is 0.5-2 hours, and heating rate is 3-8 DEG C/min.
5. preparation method as claimed in claim 4, which is characterized in that nickel salt in nickel acetate, nickel nitrate, nickel chloride one
Kind or combinations thereof；The one kind or combinations thereof of molysite in ferric acetate, ferric nitrate, iron chloride.
6. preparation method as claimed in claim 4, which is characterized in that the molal quantity of the nickel salt and the quality of graphene oxide
Ratio be：(0.016-0.04) mol/g, preferably (0.02-0.04) mol/g, more preferably 0.02mol/g.
7. preparation method as claimed in claim 4, which is characterized in that the mass ratio of the composite material precursors and the sulphur powder
It is 1:(20-40).
8. preparation method as claimed in claim 4, which is characterized in that step (3) is specially：Answer mixture in 100- by described
It is reacted 9-14 hours at 130 DEG C, is continuously heating to react 1-4 hours at 150-180 DEG C.
9. the method as described in any one of claim 4-8, which is characterized in that before step (3), further include：
Reaction mixture is stirred 2-8 hours at 50-90 DEG C, is then cooled down.
10. ferronickel sulfide-graphene composite material described in any one of claim 1-3 is used as oxygen evolution reaction elctro-catalyst
Purposes.
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| CN110721728A (en) * | 2019-11-12 | 2020-01-24 | 南京工程学院 | Supported bifunctional catalytic composite material and preparation method thereof |
| CN111097452A (en) * | 2020-01-08 | 2020-05-05 | 济南大学 | Preparation method of graphene-loaded ferrous sulfide nano material and application of graphene-loaded ferrous sulfide nano material in electrocatalytic nitrogen reduction |
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| CN114108028B (en) * | 2021-12-13 | 2023-06-20 | 聊城大学 | Efficient water oxidation FeNiS 2 rGO electrocatalyst, method for its preparation and use |
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